1-Allyl-6-nitro-1H-indazole

El Brahmi, N.; Benchidmi, M.; Essassi, E.M.; Ladeira, S.; El Ammari, L.

doi:10.1107/S1600536812046478

organic compounds

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Volume 68| Part 12| December 2012| Page o3368

doi:10.1107/S1600536812046478

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1-Allyl-6-nitro-1H-indazole

Nabil El Brahmi,^a ^* Mohammed Benchidmi,^a El Mokhtar Essassi,^a Sonia Ladeira ^b and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC21, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, ^bLaboratoire de Chimie de Coordination, route de Narbonne, 31077 Toulouse, France, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: n_elbrahmi@yahoo.fr

(Received 20 October 2012; accepted 9 November 2012; online 17 November 2012)

The fused five- and six-membered rings in the title molecule, C₁₀H₉N₃O₂, are essentially coplanar, the largest deviation from the mean plane being 0.012 (1) Å for the C atom linked to the nitro group. The fused-ring system makes a dihedral angle of 11.34 (6)° with the nitro group, leading to a syn-periplanar conformation. The plane through the atoms forming the allyl group is nearly perpendicular to the indazole fused-ring system, as indicated by the dihedral angle of 73.3 (5)°. In the crystal, each molecule is linked to its symmetry equivalent about the center of inversion by pairs of non-classical C—H⋯O hydrogen bonds, forming an extended tape motif parallel to the (-12-1) plane.

Related literature

For the pharmacological and biochemical properties of substituted indazoles, see: Saczewski et al. (2008 ); Jones et al. (2009 ); Bouissane et al. (2006 ). For compounds with similar structures, see: El Brahmi et al. (2009 , 2011 ).

Experimental

Crystal data

C₁₀H₉N₃O₂
M_r = 203.20
Triclinic, $[P \overline 1]$
a = 4.3630 (16) Å
b = 8.3245 (7) Å
c = 13.541 (5) Å
α = 95.647 (2)°
β = 98.46 (2)°
γ = 97.770 (2)°
V = 478.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.38 × 0.29 × 0.27 mm

Data collection

Bruker Kappa APEXII Quazar area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.957, T_max = 0.997
8258 measured reflections
2109 independent reflections
1675 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.100
S = 1.06
2109 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O1ⁱ	0.93	2.51	3.3973 (17)	160
C8—H8A⋯O1ⁱ	0.97	2.53	3.4475 (19)	157
C2—H2⋯O2ⁱⁱ	0.93	2.66	3.3911 (17)	136
Symmetry codes: (i) -x, -y, -z; (ii) -x+2, -y+1, -z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al. 2008 ); software used to prepare material for publication: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046478/pk2452sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046478/pk2452Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046478/pk2452Isup3.cml

checkCIF report

Comment top

Indazole derivatives constitute an exciting heterocyclic family because of their important biological activities. Thus substituted indazoles are generally found to be of pharmaceutical interest in a variety of therapeutic areas (Saczewski et al., 2008, Jones et al., 2009) and with significant cytotoxicities against human (colon and prostate) and murine (leukemia) cell lines (Bouissane et al., 2006).

The plot of the structure of the title compound shows the indazole ring system is linked to a C₃H₅ chain and to a nitro group (Fig.1). The fused-ring system is essentially planar, with a maximum deviation of 0.012 (1) Å for C1. The allyl group is nearly perpendicular to indazole plane as indicated by the torsion angle of C9 C8 N2 N3 = 88.35 (18)°. Moreover, the dihedral angle of 11.34 (6)° between the fused ring system and the nitro group lead to a synperiplanar conformation. The structure of the 1-Allyl-6-nitro-indazole is similar to that reported for the following molecules: 1-allyl-3-chloro-6-nitro-1H-indazole and 3-bromo-6-nitro-1-(prop-2-ynyl)-1H-indazole (El Brahmi et al. 2009, 2011).

In the crystal, each molecule and its symmetry equivalent through the inversion center are linked by C6–H6···O1, C8–H8B···O1 and C2–H2···O2, non-classical hydrogen bonds, which results in an extended tape motif parallel to the plane (-1 2 -1) as shown in Fig.2.

Related literature top

For the pharmacological and biochemical properties of substituted indazoles, see: Saczewski et al. (2008); Jones et al. (2009); Bouissane et al. (2006). For compounds with similar structures, see: El Brahmi et al. (2009, 2011).

Experimental top

6-nitroindazole (5 mmol) and allyl bromide (10 mmol) were reacted in THF (40 ml) in the presence of potassium carbonate (10 mmol) and tetra-n-butylammonium bromide (0.5 mmol). The mixture was stirred for 24 h, filtered, and the THF removed under vacuum. The product was separated by chromatography on silica gel with a hexane:ethyl acetate (9:1) solvent system. The compound was obtained as yellow crystals in 68% yield.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al. 2008); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. The title molecule and its symmetry equivalent through the inversion center linked by hydrogen bonds and building extended tape motifs parallel to the plane (-1 2 -1).

1-Allyl-6-nitro-1H-indazole top

Crystal data top

C₁₀H₉N₃O₂	Z = 2
M_r = 203.20	F(000) = 212
Triclinic, P1	D_x = 1.410 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.3630 (16) Å	Cell parameters from 2109 reflections
b = 8.3245 (7) Å	θ = 3.7–27.1°
c = 13.541 (5) Å	µ = 0.10 mm⁻¹
α = 95.647 (2)°	T = 296 K
β = 98.46 (2)°	Block, yellow
γ = 97.770 (2)°	0.38 × 0.29 × 0.27 mm
V = 478.5 (3) Å³

Data collection top

Bruker Kappa APEXII Quazar area-detector diffractometer	2109 independent reflections
Radiation source: microfocus sealed tube	1675 reflections with I > 2σ(I)
Multilayer optics monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.1°, θ_min = 3.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.957, T_max = 0.997	k = −10→10
8258 measured reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: difference Fourier map
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0593P)² + 0.0394P] where P = (F_o² + 2F_c²)/3
2109 reflections	(Δ/σ)_max < 0.001
136 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₀H₉N₃O₂	γ = 97.770 (2)°
M_r = 203.20	V = 478.5 (3) Å³
Triclinic, P1	Z = 2
a = 4.3630 (16) Å	Mo Kα radiation
b = 8.3245 (7) Å	µ = 0.10 mm⁻¹
c = 13.541 (5) Å	T = 296 K
α = 95.647 (2)°	0.38 × 0.29 × 0.27 mm
β = 98.46 (2)°

Data collection top

Bruker Kappa APEXII Quazar area-detector diffractometer	2109 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1675 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.997	R_int = 0.021
8258 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.06	Δρ_max = 0.18 e Å⁻³
2109 reflections	Δρ_min = −0.20 e Å⁻³
136 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against all reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on all data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5250 (3)	0.28071 (13)	0.07294 (8)	0.0285 (3)
C2	0.7333 (3)	0.42576 (14)	0.10756 (9)	0.0336 (3)
H2	0.8493	0.4767	0.0639	0.040*
C3	0.7649 (3)	0.49196 (14)	0.20582 (9)	0.0347 (3)
H3	0.9001	0.5887	0.2297	0.042*
C4	0.5890 (3)	0.41073 (13)	0.26971 (9)	0.0296 (3)
C5	0.3813 (3)	0.26597 (13)	0.23161 (8)	0.0269 (3)
C6	0.3433 (3)	0.19722 (13)	0.13128 (8)	0.0279 (3)
H6	0.2053	0.1020	0.1061	0.034*
C7	0.5573 (3)	0.43449 (15)	0.37259 (9)	0.0357 (3)
H7	0.6669	0.5214	0.4182	0.043*
C8	0.0238 (3)	0.06785 (15)	0.31003 (9)	0.0337 (3)
H8A	−0.1083	0.0416	0.2447	0.040*
H8B	−0.1104	0.0882	0.3595	0.040*
C9	0.1822 (3)	−0.07536 (15)	0.33350 (11)	0.0430 (3)
H9	0.3288	−0.1040	0.2942	0.052*
C10	0.1274 (4)	−0.16305 (18)	0.40592 (12)	0.0599 (4)
H10A	0.2369	−0.2555	0.4167	0.072*
H10B	−0.0296	−0.1344	0.4488	0.072*
N1	0.5029 (2)	0.21201 (12)	−0.03272 (7)	0.0335 (3)
N2	0.2434 (2)	0.21521 (11)	0.30948 (7)	0.0306 (2)
N3	0.3528 (3)	0.31791 (12)	0.39570 (7)	0.0360 (3)
O1	0.2915 (2)	0.09935 (12)	−0.06728 (7)	0.0468 (3)
O2	0.6971 (3)	0.26879 (12)	−0.08121 (7)	0.0515 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0332 (6)	0.0299 (5)	0.0236 (6)	0.0101 (5)	0.0050 (5)	0.0012 (4)
C2	0.0385 (7)	0.0296 (6)	0.0340 (6)	0.0042 (5)	0.0099 (5)	0.0051 (5)
C3	0.0399 (7)	0.0263 (5)	0.0361 (7)	0.0005 (5)	0.0068 (5)	0.0003 (5)
C4	0.0342 (6)	0.0265 (5)	0.0271 (6)	0.0064 (5)	0.0028 (5)	−0.0015 (4)
C5	0.0279 (5)	0.0280 (5)	0.0255 (6)	0.0073 (4)	0.0036 (4)	0.0031 (4)
C6	0.0290 (6)	0.0276 (5)	0.0257 (6)	0.0046 (4)	0.0018 (4)	−0.0008 (4)
C7	0.0429 (7)	0.0339 (6)	0.0266 (6)	0.0020 (5)	0.0029 (5)	−0.0044 (5)
C8	0.0300 (6)	0.0421 (6)	0.0261 (6)	−0.0028 (5)	0.0041 (5)	0.0023 (5)
C9	0.0370 (7)	0.0356 (7)	0.0521 (8)	−0.0037 (5)	0.0074 (6)	−0.0032 (6)
C10	0.0817 (12)	0.0388 (7)	0.0518 (9)	0.0053 (8)	−0.0079 (8)	0.0024 (7)
N1	0.0409 (6)	0.0351 (5)	0.0263 (5)	0.0117 (4)	0.0070 (4)	0.0021 (4)
N2	0.0343 (5)	0.0336 (5)	0.0223 (5)	0.0018 (4)	0.0048 (4)	0.0005 (4)
N3	0.0426 (6)	0.0387 (6)	0.0240 (5)	0.0034 (5)	0.0036 (4)	−0.0031 (4)
O1	0.0512 (6)	0.0529 (6)	0.0297 (5)	−0.0007 (5)	0.0020 (4)	−0.0088 (4)
O2	0.0659 (7)	0.0549 (6)	0.0364 (5)	0.0031 (5)	0.0255 (5)	0.0017 (4)

Geometric parameters (Å, º) top

C1—C6	1.3706 (16)	C7—H7	0.9300
C1—C2	1.4036 (17)	C8—N2	1.4522 (15)
C1—N1	1.4720 (15)	C8—C9	1.4942 (18)
C2—C3	1.3691 (17)	C8—H8A	0.9700
C2—H2	0.9300	C8—H8B	0.9700
C3—C4	1.4016 (16)	C9—C10	1.309 (2)
C3—H3	0.9300	C9—H9	0.9300
C4—C5	1.4087 (15)	C10—H10A	0.9711
C4—C7	1.4174 (17)	C10—H10B	0.9983
C5—N2	1.3631 (14)	N1—O2	1.2203 (13)
C5—C6	1.3985 (16)	N1—O1	1.2256 (14)
C6—H6	0.9300	N2—N3	1.3605 (14)
C7—N3	1.3204 (16)

C6—C1—C2	124.41 (11)	C4—C7—H7	124.2
C6—C1—N1	117.64 (10)	N2—C8—C9	112.95 (10)
C2—C1—N1	117.95 (10)	N2—C8—H8A	109.0
C3—C2—C1	119.75 (11)	C9—C8—H8A	109.0
C3—C2—H2	120.1	N2—C8—H8B	109.0
C1—C2—H2	120.1	C9—C8—H8B	109.0
C2—C3—C4	118.53 (11)	H8A—C8—H8B	107.8
C2—C3—H3	120.7	C10—C9—C8	124.06 (14)
C4—C3—H3	120.7	C10—C9—H9	118.0
C3—C4—C5	119.81 (11)	C8—C9—H9	118.0
C3—C4—C7	136.30 (11)	C9—C10—H10A	119.9
C5—C4—C7	103.89 (10)	C9—C10—H10B	119.2
N2—C5—C6	130.53 (10)	H10A—C10—H10B	120.9
N2—C5—C4	106.94 (10)	O2—N1—O1	123.28 (10)
C6—C5—C4	122.53 (10)	O2—N1—C1	118.53 (10)
C1—C6—C5	114.96 (10)	O1—N1—C1	118.18 (10)
C1—C6—H6	122.5	N3—N2—C5	111.12 (10)
C5—C6—H6	122.5	N3—N2—C8	120.52 (9)
N3—C7—C4	111.61 (11)	C5—N2—C8	128.23 (9)
N3—C7—H7	124.2	C7—N3—N2	106.44 (10)

C6—C1—C2—C3	0.27 (18)	N2—C8—C9—C10	125.37 (14)
N1—C1—C2—C3	−178.80 (10)	C6—C1—N1—O2	−168.29 (10)
C1—C2—C3—C4	0.77 (17)	C2—C1—N1—O2	10.84 (16)
C2—C3—C4—C5	−1.17 (16)	C6—C1—N1—O1	11.05 (16)
C2—C3—C4—C7	178.55 (13)	C2—C1—N1—O1	−169.83 (10)
C3—C4—C5—N2	−179.75 (10)	C6—C5—N2—N3	178.95 (11)
C7—C4—C5—N2	0.45 (12)	C4—C5—N2—N3	−0.67 (12)
C3—C4—C5—C6	0.59 (16)	C6—C5—N2—C8	3.07 (19)
C7—C4—C5—C6	−179.21 (10)	C4—C5—N2—C8	−176.55 (11)
C2—C1—C6—C5	−0.84 (16)	C9—C8—N2—N3	−88.19 (13)
N1—C1—C6—C5	178.23 (9)	C9—C8—N2—C5	87.34 (14)
N2—C5—C6—C1	−179.17 (10)	C4—C7—N3—N2	−0.31 (14)
C4—C5—C6—C1	0.40 (15)	C5—N2—N3—C7	0.62 (13)
C3—C4—C7—N3	−179.84 (13)	C8—N2—N3—C7	176.85 (10)
C5—C4—C7—N3	−0.09 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.51	3.3973 (17)	160
C8—H8A···O1ⁱ	0.97	2.53	3.4475 (19)	157
C2—H2···O2ⁱⁱ	0.93	2.66	3.3911 (17)	136

Symmetry codes: (i) −x, −y, −z; (ii) −x+2, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₀H₉N₃O₂
M_r	203.20
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	4.3630 (16), 8.3245 (7), 13.541 (5)
α, β, γ (°)	95.647 (2), 98.46 (2), 97.770 (2)
V (Å³)	478.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.38 × 0.29 × 0.27

Data collection
Diffractometer	Bruker Kappa APEXII Quazar area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.957, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	8258, 2109, 1675
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.100, 1.06
No. of reflections	2109
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.20

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al. 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O1ⁱ	0.93	2.51	3.3973 (17)	160.0
C8—H8A···O1ⁱ	0.97	2.53	3.4475 (19)	157.3
C2—H2···O2ⁱⁱ	0.93	2.66	3.3911 (17)	135.7

Symmetry codes: (i) −x, −y, −z; (ii) −x+2, −y+1, −z.

References

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